CN116969506A - Electrolyte material for solid oxide fuel cell and preparation method thereof - Google Patents
Electrolyte material for solid oxide fuel cell and preparation method thereof Download PDFInfo
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- CN116969506A CN116969506A CN202311242596.1A CN202311242596A CN116969506A CN 116969506 A CN116969506 A CN 116969506A CN 202311242596 A CN202311242596 A CN 202311242596A CN 116969506 A CN116969506 A CN 116969506A
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- 239000002001 electrolyte material Substances 0.000 title claims abstract description 123
- 239000000446 fuel Substances 0.000 title claims abstract description 56
- 239000007787 solid Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 159
- 150000003839 salts Chemical class 0.000 claims abstract description 151
- 239000002904 solvent Substances 0.000 claims abstract description 145
- 238000000034 method Methods 0.000 claims abstract description 139
- 238000005245 sintering Methods 0.000 claims abstract description 108
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 106
- 230000008569 process Effects 0.000 claims abstract description 102
- -1 lithium halide Chemical class 0.000 claims abstract description 98
- 239000000843 powder Substances 0.000 claims abstract description 84
- 238000002156 mixing Methods 0.000 claims abstract description 71
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 49
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 42
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims description 44
- 239000000919 ceramic Substances 0.000 claims description 34
- 229910052708 sodium Inorganic materials 0.000 claims description 27
- 239000011734 sodium Substances 0.000 claims description 27
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 229910001507 metal halide Inorganic materials 0.000 claims description 26
- 150000005309 metal halides Chemical class 0.000 claims description 26
- 229910052700 potassium Inorganic materials 0.000 claims description 25
- 239000011591 potassium Substances 0.000 claims description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 7
- 239000001103 potassium chloride Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 abstract description 37
- 230000006911 nucleation Effects 0.000 abstract description 32
- 238000010899 nucleation Methods 0.000 abstract description 32
- 238000002844 melting Methods 0.000 abstract description 25
- 230000008018 melting Effects 0.000 abstract description 25
- 230000002194 synthesizing effect Effects 0.000 abstract description 16
- 238000000465 moulding Methods 0.000 abstract description 6
- 238000004134 energy conservation Methods 0.000 abstract 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 32
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 17
- 229910001928 zirconium oxide Inorganic materials 0.000 description 17
- 230000009286 beneficial effect Effects 0.000 description 15
- 229910052736 halogen Inorganic materials 0.000 description 15
- 150000002367 halogens Chemical class 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 229910052727 yttrium Inorganic materials 0.000 description 14
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 14
- 238000000354 decomposition reaction Methods 0.000 description 12
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 229910001508 alkali metal halide Inorganic materials 0.000 description 10
- 150000008045 alkali metal halides Chemical class 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 7
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000012063 pure reaction product Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 238000011534 incubation Methods 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
Abstract
The invention provides an electrolyte material of a solid oxide fuel cell and a preparation method thereof, which relate to the technical field of preparation of electrolyte materials, and the preparation method comprises the following steps: preparing a molten salt solvent with lithium element; preparing a powder reagent consisting of zirconium nitrate and yttrium oxide; mixing the powder reagent with a molten salt solvent to obtain a mixed material; sintering the mixed material to obtain an intermediate material; pouring the intermediate material into water, and obtaining the electrolyte material after the treatment process. According to the technical scheme, the electrolyte material is synthesized by adopting a molten salt method, the preparation method is simple, the molding size of the electrolyte material is optimized, and the requirements of micro-nano size and uniformity can be met. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material, the halide of lithium element is taken as a nucleation point, the overall morphology is bowl-shaped, the nucleation is facilitated in the sintering process, and in the sintering process, the melting point can be lower, so that energy conservation is facilitated in the preparation process.
Description
Technical Field
The invention relates to the technical field of preparation of electrolyte materials, in particular to a preparation method of an electrolyte material of a solid oxide fuel cell and the electrolyte material of the solid oxide fuel cell.
Background
For the electrolyte layer of the solid oxide fuel cell, a better compactness is required. For electrolyte materials for preparing the electrolyte layer (e.g., YSZ, a type of zirconia doped with rare earth yttrium, often referred to as yttrium stabilized zirconia), conventional preparation methods are sintering, electrofusion, solvothermal methods, chemical methods, precipitation methods, and the like. The electrolyte material prepared by sintering is liable to have the following problems: the obtained electrolyte material is not sufficiently sintered, and micro-nano size is difficult to form or achieve uniformity. The preparation process of the electrolyte material obtained by electrofusion, solvothermal method, chemical method or precipitation method is complex. How to simplify the preparation process and optimize the molding size of the obtained electrolyte material is a problem to be solved at present.
Disclosure of Invention
In order to solve or improve the technical problems that the preparation process is complex and the molding size of the obtained electrolyte material cannot be optimized, the invention aims to provide a preparation method of the electrolyte material of a solid oxide fuel cell.
Another object of the present invention is to provide an electrolyte material for a solid oxide fuel cell.
To achieve the above object, a first aspect of the present invention provides a method for producing an electrolyte material for a solid oxide fuel cell, comprising: preparing a molten salt solvent consisting of a metal halide; preparing a powder reagent consisting of zirconium nitrate and yttrium oxide; mixing the powder reagent with a molten salt solvent to obtain a mixed material; sintering the mixed material to obtain an intermediate material; pouring the intermediate material into water, and obtaining the electrolyte material after the treatment process.
According to the technical scheme of the preparation method of the electrolyte material of the solid oxide fuel cell, the electrolyte material is synthesized by adopting a molten salt method, and the preparation method is simple; in the second aspect, the forming size of the electrolyte material is optimized, and the requirements of micro-nano size and uniformity can be met. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material, the halide of lithium element is taken as a nucleation point, and the overall morphology is bowl-shaped, so that nucleation in the sintering process is facilitated. In addition, as the molten salt solvent contains lithium element, the melting point can be lower when sintering is carried out, which is beneficial to realizing energy saving in the preparation process.
A solid oxide fuel cell (Solid Oxide Fuel Cell, abbreviated as SOFC) belongs to a third generation fuel cell, and is an all-solid-state chemical power generation device capable of directly converting chemical energy stored in fuel and oxidant into electric energy at medium and high temperatures with high efficiency.
Specifically, the method for producing an electrolyte material for a solid oxide fuel cell comprises the steps of:
in the first step, a molten salt solvent having lithium element is prepared. Molten salts are melts formed after melting salts, for example alkali metal, alkaline earth metal halides, nitrates, sulfates. Alternatively, the lava solvent is composed of a metal halide, and the metal halide includes lithium halide, so that the lava solvent has a lithium element. Among the binary compounds containing halogen, compounds in which halogen (halogen element including fluorine element, chlorine element, bromine element and iodine element) is negatively charged are called halides. The metallic halides and the nonmetallic halides are classified according to the properties of the constituent halide elements. Most of the alkali metal halides and alkaline earth metal halides are ionic, and are characterized by high melting point and boiling point, and are easily dissolved in water. Alternatively, the metal halide in this step is an ionic alkali metal halide and the intermediate material is poured into water in a subsequent step to remove the molten salt solvent. Optionally, lithium halide is combined with halides of other metals in a ratio of the amounts of the substances in the molten salt solvent. In the technical scheme defined by the invention, the electrolyte material is synthesized by adopting a molten salt method. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material in the subsequent step, the halide of lithium element is taken as a nucleation point, and the overall morphology is bowl-shaped, so that nucleation in the sintering process is facilitated. In addition, since the molten salt solvent contains lithium element, the melting point can be lower (may be 750 ℃ at the minimum) when sintering is performed in the subsequent step, contributing to energy saving in the manufacturing process.
In the second step, a catalyst prepared from zirconium nitrate Zr (NO 3 ) 4 Yttria Y 2 O 3 Powder reagent is formed. Optionally, zirconium nitrate and yttrium oxide are mixed according to an atomic ratio of 100:4, mixing the components in proportion to obtain the powder reagent. The main purpose of adding zirconium nitrate is to provide zirconium element, and zirconium nitrate can be decomposed into zirconium oxide in the subsequent step; the main purpose of adding yttria is to provide yttrium element to the reactants.
And thirdly, mixing the powder reagent with the molten salt solvent to obtain a mixed material. Optionally, mixing the powder reagent and the molten salt solvent through a mixer to obtain a mixed material. Optionally, the ambient temperature during compounding is from 90 ℃ to 120 ℃; the rotating speed of the mixer is 100r/min to 200r/min in the mixing process; the mixing time is 2 to 10 hours. Alternatively, zirconium nitrate can be decomposed into zirconium oxide under the action of mechanical and thermal energy at an ambient temperature of 120 ℃, and the physical size of the substance becomes smaller due to the existence of ball milling during the mixing process. In the mixing process, the components tend to be homogenized, and the refinement of particles and microcosmic can be realized; during the mixing process, chemical reactions, such as decomposition reactions (the decomposition of zirconium nitrate into zirconium oxide) also occur.
And step four, sintering the mixed material to obtain an intermediate material. Sintering is a process of converting a powdery material into a compact. After the powder is formed, the compact obtained by sintering is a polycrystalline material. The sintering process directly affects the grain size, pore size, and grain boundary shape and distribution in the microstructure, thereby affecting the properties of the material. Optionally, the mixed material is filled into a ceramic pot for sealing, and the ceramic pot filled with the mixed material is placed into a muffle furnace for sintering. Muffle furnace is box furnace. Optionally, during sintering, the ambient temperature is 750 ℃ to 950 ℃ and the incubation time is 4 hours to 20 hours.
And fifthly, pouring the intermediate material into water, and obtaining the electrolyte material after the treatment process. Optionally, pouring the intermediate material into clear water, and obtaining the micro-nano YSZ powder through a series of treatment processes such as centrifugation, filtration, drying and the like. The micro-nano YSZ powder is the electrolyte material. YSZ represents a class of rare earth yttrium doped zirconia, also known as yttrium stabilized zirconia. The purpose of pouring the intermediate material into the clear water in this step is to remove the molten salt solvent.
In the technical scheme defined by the invention, the electrolyte material is synthesized by adopting a molten salt method, and the preparation method is simple in the first aspect; in the second aspect, the forming size of the electrolyte material is optimized, and the requirements of micro-nano size and uniformity can be met. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material, the halide of lithium element is taken as a nucleation point, and the overall morphology is bowl-shaped, so that nucleation in the sintering process is facilitated. In addition, as the molten salt solvent contains lithium element, the melting point can be lower when sintering is carried out, which is beneficial to realizing energy saving in the preparation process.
The electrolyte material prepared by the preparation method has specific advantages in structure and morphology, namely, the YSZ powder prepared by the molten salt method has specific advantages compared with the YSZ powder prepared by the traditional sintering method. The YSZ powder prepared by the molten salt method has high matching property with the ethanol solvent, and is suitable for suspension slurry used in the plasma spraying process. In addition, suspension of YSZ powder prepared by the molten salt method can keep lasting (about 8 hours) suspension characteristics.
In addition, the technical scheme provided by the invention can also have the following additional technical characteristics:
in some embodiments, optionally, a molten salt solvent with lithium element is prepared, specifically: a molten salt solvent is prepared that consists of a metal halide that includes lithium halide.
In this technical scheme, the lava solvent is composed of a metal halide, and the metal halide includes lithium halide, so that the lava solvent has lithium element. Among the binary compounds containing halogen, compounds in which halogen (halogen element including fluorine element, chlorine element, bromine element and iodine element) is negatively charged are called halides. The metallic halides and the nonmetallic halides are classified according to the properties of the constituent halide elements. Most of the alkali metal halides and alkaline earth metal halides are ionic, and are characterized by high melting point and boiling point, and are easily dissolved in water. Alternatively, the metal halide in this step is an ionic alkali metal halide and the intermediate material is poured into water in a subsequent step to remove the molten salt solvent. Optionally, lithium halide is combined with halides of other metals in a ratio of the amounts of the substances in the molten salt solvent. In the technical scheme defined by the invention, the electrolyte material is synthesized by adopting a molten salt method. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material in the subsequent step, the halide of lithium element is taken as a nucleation point, and the overall morphology is bowl-shaped, so that nucleation in the sintering process is facilitated. In addition, since the molten salt solvent contains lithium element, the melting point can be lower (may be 750 ℃ at the minimum) when sintering is performed in the subsequent step, contributing to energy saving in the manufacturing process.
In some embodiments, optionally, the metal halide further comprises sodium halide.
In this technical scheme, sodium halide is used as a main molten salt solvent, zirconium nitrate and yttrium oxide are reacted in a liquid phase environment and a desired product (intermediate material) is produced. Sodium halide as one of the solvents may act as a dispersing compound. In the subsequent step, the intermediate material is poured into water to remove the redundant molten salt solvent, so as to obtain a pure reaction product. Alternatively, the sodium halide is sodium chloride.
In some embodiments, optionally, the metal halide further comprises potassium halide.
In this technical scheme, potassium halide is used as a main molten salt solvent, zirconium nitrate and yttrium oxide are reacted in a liquid phase environment and a desired product (intermediate material) is produced. In the subsequent step, the intermediate material is poured into water to remove the redundant molten salt solvent, so as to obtain a pure reaction product. Alternatively, the potassium halide is potassium chloride.
In some embodiments, optionally, the proportional relationship between the amount of the sodium halide substance, the amount of the potassium halide substance, and the amount of the lithium halide substance is (1-3): (1-4): (1-5).
In this technical scheme, the amount of the substance of lithium halide is one eighth to five seventh of the amount of the substance of the molten salt solvent. By controlling the ratio of the amount of lithium halide in the molten salt solvent, on the one hand, it can be ensured that the molten salt solvent contains a sufficient amount of lithium halide (a sufficient amount of lithium element); on the other hand, excessive amounts of lithium halide species can be avoided, which is advantageous in cost control. Alternatively, the lithium halide is lithium chloride. The molten salt solvent comprises lithium chloride, and lithium chloride is taken as a nucleation point in the process of synthesizing the electrolyte material, so that the overall morphology is bowl-shaped, and nucleation in the sintering process is facilitated. In addition, as the molten salt solvent contains lithium element, the melting point can be lower when sintering is carried out, which is beneficial to realizing energy saving in the preparation process.
Further, the amount of sodium halide substance is one tenth to three fifths of the amount of molten salt solvent substance. By controlling the ratio of the amount of sodium halide in the molten salt solvent, on the one hand, it can be ensured that the molten salt solvent contains enough sodium halide; on the other hand, excessive amounts of sodium halide substances can be avoided, which is beneficial to cost control.
Further, the amount of the substance of potassium halide is one-ninth to two-thirds of the amount of the substance of the molten salt solvent. By controlling the ratio of the amount of potassium halide in the molten salt solvent, on the one hand, it can be ensured that the molten salt solvent contains enough potassium halide; on the other hand, excessive amounts of potassium halide substances can be avoided, which is beneficial to cost control.
In some embodiments, the lithium halide is optionally lithium chloride.
In the technical scheme, the molten salt solvent comprises lithium chloride, and lithium chloride is taken as a nucleation point in the process of synthesizing the electrolyte material, so that the overall morphology is bowl-shaped, and nucleation in the sintering process is facilitated.
In some embodiments, the sodium halide is sodium chloride.
In the technical scheme, sodium chloride is used as a main molten salt solvent, and can play a role of dispersing a compound, so that zirconium nitrate and yttrium oxide react in a liquid phase environment to generate a required product (intermediate material).
In some embodiments, the potassium halide is potassium chloride.
In this technical scheme, potassium chloride is used as the main molten salt solvent, zirconium nitrate and yttrium oxide are reacted in a liquid phase environment and the desired product (intermediate material) is produced. In the subsequent step, the intermediate material is poured into water to remove the redundant molten salt solvent, so as to obtain a pure reaction product.
In some technical solutions, optionally, a powder reagent consisting of zirconium nitrate and yttrium oxide is prepared, specifically: zirconium nitrate and yttrium oxide are mixed according to the atomic ratio of 100:4, mixing the components in proportion to obtain the powder reagent.
In the technical scheme, the atomic ratio of molecular formula after the formation of the pre-powder is determined by controlling the mixing proportion of zirconium nitrate and yttrium oxide so as to prepare the YSZ powder.
In some technical schemes, optionally, powder reagents and molten salt solvents are mixed to obtain a mixed material, specifically: and mixing the powder reagent and the molten salt solvent through a mixer to obtain a mixed material.
In the technical scheme, the powder reagent and the molten salt solvent are fully mixed by a mixer. In addition, by controlling the temperature, the rotating speed and the time during mixing, the powder reagent and the molten salt solvent can be ensured to be fully mixed under proper conditions.
In some technical schemes, optionally, powder reagents and molten salt solvents are mixed by a mixer to obtain mixed materials, specifically: and (3) mixing the powder reagent and the molten salt solvent by a mixer at a first temperature threshold and a first rotation speed threshold for a first time threshold, so as to obtain a mixed material.
In the technical scheme, the powder reagent and the molten salt solvent can be fully mixed under proper conditions by controlling the temperature, the rotating speed and the time during mixing.
In some embodiments, optionally, the first temperature threshold is 90 ℃ to 120 ℃.
In the technical scheme, the environment temperature during mixing is controlled to be 90-120 ℃, so that on one hand, the environment temperature is not too low, and the powder reagent and the molten salt solvent can be fully mixed under proper conditions; on the other hand, the environment temperature is not too high, which is beneficial to controlling the energy consumption.
In some embodiments, optionally, the first rotational speed threshold is 100r/min to 200r/min.
In the technical scheme, the rotating speed of the mixer is controlled to be 100r/min to 200r/min, so that on one hand, the excessive high rotating speed of the mixer can be avoided, and the energy consumption can be controlled; on the other hand, the over-slow rotation speed of the mixer can be avoided, so that the powder reagent and the molten salt solvent can be fully mixed under the assistance of the mixer.
In some embodiments, optionally, the first time threshold is 2h to 10h.
In the technical scheme, the mixing time is controlled to be 2-10 hours, so that on one hand, the too short mixing time can be avoided, and the powder reagent and the molten salt solvent can be fully mixed under the assistance of a mixer; on the other hand, the overlong mixing time can be avoided, so that the overall preparation efficiency is improved.
In some embodiments, the mixture is optionally sintered to obtain an intermediate material, specifically: sintering the mixed material at a second temperature threshold, and preserving heat for a second time threshold to obtain the intermediate material.
In the technical scheme, the intermediate material is ensured to be prepared for the subsequent steps by controlling the temperature and the heat preservation time in the sintering process. The temperature and the heat preservation time during sintering can be accurately controlled, and the forming size of the electrolyte material can be optimized to a certain extent.
In some embodiments, optionally, the second temperature threshold is 750 ℃ to 950 ℃.
In the technical scheme, the temperature during sintering is controlled to be 750-950 ℃, so that on one hand, the overhigh temperature can be avoided, and the energy consumption can be controlled; on the other hand, too low a temperature can be avoided, thereby ensuring that intermediate materials are prepared after sintering for use in subsequent steps. Since the molten salt solvent contains lithium element, the melting point can be lower (at least 750 ℃) when sintering is performed in the subsequent step, which contributes to energy saving in the manufacturing process.
In some embodiments, optionally, the second time threshold is 4h to 20h.
In the technical scheme, the heat preservation time in the sintering process is controlled to be 4-20 hours, so that on one hand, the heat preservation time can be prevented from being too short, and the preparation of the intermediate material after full sintering is ensured; on the other hand, the overlong heat preservation time of sintering can be avoided, so that the overall preparation efficiency is improved.
In some technical schemes, optionally, sintering the mixed material at a second temperature threshold, and preserving heat for a second time threshold to obtain an intermediate material, specifically: and filling the mixed material into a ceramic pot for sealing, putting the ceramic pot filled with the mixed material into a muffle furnace for sintering at a second temperature threshold, and preserving heat for a second time threshold to obtain the intermediate material.
In the technical scheme, the mixed materials are filled into the ceramic pot for sealing, so that the mixed materials are ensured not to react with the outside air in the sintering process, and irrelevant factors are eliminated. In addition, the ceramic pot filled with the mixed materials is placed into a muffle furnace for sintering, so that the sufficiency of the sintering process is ensured, and the intermediate materials are prepared for subsequent steps.
In some embodiments, optionally, the ceramic tank is made of alumina.
In the technical scheme, the ceramic tank is made of alumina, so that the mixed material which can be filled into the ceramic tank is sealed, and the mixed material is ensured not to react with the outside air in the sintering process, so that irrelevant factors are eliminated.
In some embodiments, optionally, the ceramic tank is made of zirconia.
In the technical scheme, the ceramic tank is made of zirconia, so that the mixed material which can be filled into the ceramic tank is sealed, and the mixed material is ensured not to react with external air in the sintering process, so that irrelevant factors are eliminated.
In some technical schemes, optionally, pouring the intermediate material into water, and obtaining the electrolyte material after the treatment process, specifically: pouring the intermediate material into water, centrifuging, filtering and drying to obtain the electrolyte material.
In this solution, the purpose of centrifugation is to separate the different suspended particles effectively. Further, the purpose of the filtration is, on the one hand, to remove impurities, ensuring the purity of the electrolyte material prepared; on the other hand, the particle size is screened, so that the micro-nano YSZ powder is ensured to be obtained, the forming size of the electrolyte material is optimized, and the requirements of micro-nano size and uniformity are met. Further, the purpose of the drying is to remove water molecules to exclude extraneous factors.
The second aspect of the invention provides an electrolyte material of a solid oxide fuel cell, which is prepared by the preparation method of the electrolyte material of the solid oxide fuel cell in any one of the technical schemes.
According to the technical scheme of the electrolyte material of the solid oxide fuel cell, the electrolyte material of the solid oxide fuel cell is manufactured by the preparation method of the electrolyte material of the solid oxide fuel cell in any one of the technical scheme. The electrolyte material prepared by the preparation method provided by the invention has uniform molding size and meets the requirements of micro-nano size and uniformity.
Additional aspects and advantages of the present invention will be made apparent from the description which follows, or may be learned by practice of the invention.
Drawings
Fig. 1 shows a flowchart of a method of preparing an electrolyte material of a solid oxide fuel cell according to a first embodiment of the present invention;
fig. 2 shows a flowchart of a method of preparing an electrolyte material of a solid oxide fuel cell according to a second embodiment of the present invention;
fig. 3 shows a flowchart of a method for producing an electrolyte material of a solid oxide fuel cell according to a third embodiment of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of embodiments of the present application can be more clearly understood, a further detailed description of embodiments of the present application will be rendered by reference to the appended drawings and detailed description thereof. It should be noted that, without conflict, the embodiments of the present application and features in the embodiments may be combined with each other.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, however, embodiments of the application may be practiced otherwise than as described herein, and therefore the scope of the application is not limited to the specific embodiments disclosed below.
An electrolyte material of a solid oxide fuel cell and a method of manufacturing the same according to some embodiments of the present application are described below with reference to fig. 1 to 3.
A solid oxide fuel cell (Solid Oxide Fuel Cell, abbreviated as SOFC) belongs to a third generation fuel cell, and is an all-solid-state chemical power generation device capable of directly converting chemical energy stored in fuel and oxidant into electric energy at medium and high temperatures with high efficiency.
In a first embodiment according to the present application, as shown in fig. 1, the steps of the method for preparing an electrolyte material of a solid oxide fuel cell include:
S102, preparing a molten salt solvent with lithium element. Molten salts are melts formed after melting salts, for example alkali metal, alkaline earth metal halides, nitrates, sulfates. Alternatively, the lava solvent is composed of a metal halide, and the metal halide includes lithium halide, so that the lava solvent has a lithium element. Among the binary compounds containing halogen, compounds in which halogen (halogen element including fluorine element, chlorine element, bromine element, iodine element) is negatively charged are called halides. The metallic halides and the nonmetallic halides are classified according to the properties of the constituent halide elements. Most of the alkali metal halides and alkaline earth metal halides are ionic, and are characterized by high melting point and boiling point, and are easily dissolved in water. Alternatively, the metal halide in this step is an ionic alkali metal halide and the intermediate material is poured into water in a subsequent step to remove the molten salt solvent. Alternatively, in the molten salt solvent, the lithium halide and the halide of other metals constitute the molten salt solvent in a ratio of the amounts of the substances. In the technical scheme defined by the invention, the electrolyte material is synthesized by adopting a molten salt method. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material in the subsequent step, the halide of lithium element is taken as a nucleation point, and the overall morphology is bowl-shaped, so that nucleation in the sintering process is facilitated. In addition, since the molten salt solvent contains lithium element, the melting point can be lower (may be 750 ℃ at the minimum) when sintering is performed in the subsequent step, contributing to energy saving in the manufacturing process.
S104, preparation of zirconium nitrate Zr (NO) 3 ) 4 Yttria Y 2 O 3 Powder reagent is formed. Optionally, zirconium nitrate and yttrium oxide are mixed according to an atomic ratio of 100:4, mixing the components in proportion to obtain the powder reagent. The main purpose of adding zirconium nitrate is to provide zirconium element, and zirconium nitrate can be decomposed into zirconium oxide in the subsequent step; the main purpose of adding yttria is to provide yttrium element to the reactants.
S106, mixing the powder reagent with the molten salt solvent to obtain a mixed material. Optionally, mixing the powder reagent and the molten salt solvent through a mixer to obtain a mixed material. Optionally, the ambient temperature during compounding is from 90 ℃ to 120 ℃; the rotating speed of the mixer is 100r/min to 200r/min in the mixing process; the mixing time is 2 to 10 hours. Alternatively, zirconium nitrate can be decomposed into zirconium oxide under the action of mechanical and thermal energy at an ambient temperature of 120 ℃, and the physical size of the substance becomes smaller due to the existence of ball milling during the mixing process. In the mixing process, the components tend to be homogenized, and the refinement of particles and microcosmic can be realized; during the mixing process, chemical reactions, such as decomposition reactions (the decomposition of zirconium nitrate into zirconium oxide) also occur.
S108, sintering the mixed material to obtain an intermediate material. Sintering is a process of converting a powdery material into a compact. After the powder is formed, the compact obtained by sintering is a polycrystalline material. The sintering process directly affects the grain size, pore size, and grain boundary shape and distribution in the microstructure, thereby affecting the properties of the material. Optionally, the mixed material is filled into a ceramic pot for sealing, and the ceramic pot filled with the mixed material is placed into a muffle furnace for sintering. Muffle furnace is box furnace. Optionally, during sintering, the ambient temperature is 750 ℃ to 950 ℃ and the incubation time is 4 hours to 20 hours.
S110, pouring the intermediate material into water, and obtaining the electrolyte material after the treatment process. Optionally, pouring the intermediate material into clear water, and obtaining the micro-nano YSZ powder through a series of treatment processes such as centrifugation, filtration, drying and the like. The micro-nano YSZ powder is the electrolyte material. The purpose of pouring the intermediate material into the clear water in this step is to remove the molten salt solvent.
As can be seen from the above table, the preparation method of the present invention (preparation method of electrolyte material of solid oxide fuel cell) optimizes the molding size of the electrolyte material compared with the solid phase sintering method, and can meet the requirements of micro-nano size and uniformity.
In the technical scheme defined by the invention, the electrolyte material is synthesized by adopting a molten salt method, and the preparation method is simple in the first aspect; in the second aspect, the forming size of the electrolyte material is optimized, and the requirements of micro-nano size and uniformity can be met. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material, the halide of lithium element is taken as a nucleation point, and the overall morphology is bowl-shaped, so that nucleation in the sintering process is facilitated. In addition, as the molten salt solvent contains lithium element, the melting point can be lower when sintering is carried out, which is beneficial to realizing energy saving in the preparation process.
The electrolyte material prepared by the preparation method has specific advantages in structure and morphology, namely, the YSZ powder prepared by the molten salt method has specific advantages compared with the YSZ powder prepared by the traditional sintering method. The YSZ powder prepared by the molten salt method has high matching property with the ethanol solvent, and is suitable for suspension slurry used in the plasma spraying process. In addition, suspension of YSZ powder prepared by the molten salt method can keep lasting (about 8 hours) suspension characteristics.
In a second embodiment according to the present invention, as shown in fig. 2, the steps of the method for preparing an electrolyte material of a solid oxide fuel cell include:
S202, preparing a molten salt solvent composed of metal halides, wherein the metal halides comprise lithium halides. The lava solvent is composed of a metal halide, and the metal halide includes lithium halide, so that the lava solvent has a lithium element. Among the binary compounds containing halogen, compounds in which halogen (halogen element including fluorine element, chlorine element, bromine element and iodine element) is negatively charged are called halides. The metallic halides and the nonmetallic halides are classified according to the properties of the constituent halide elements. Most of the alkali metal halides and alkaline earth metal halides are ionic, and are characterized by high melting point and boiling point, and are easily dissolved in water. Alternatively, the metal halide in this step is an ionic alkali metal halide and the intermediate material is poured into water in a subsequent step to remove the molten salt solvent. Optionally, lithium halide is combined with halides of other metals in a ratio of the amounts of the substances in the molten salt solvent. In the technical scheme defined by the invention, the electrolyte material is synthesized by adopting a molten salt method. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material in the subsequent step, the halide of lithium element is taken as a nucleation point, and the overall morphology is bowl-shaped, so that nucleation in the sintering process is facilitated. In addition, since the molten salt solvent contains lithium element, the melting point can be lower (may be 750 ℃ at the minimum) when sintering is performed in the subsequent step, contributing to energy saving in the manufacturing process.
S204, zirconium nitrate and yttrium oxide are mixed according to an atomic ratio of 100:4, mixing the components in proportion to obtain the powder reagent. And determining the atomic ratio of molecular formula after the pre-powder is formed by controlling the mixing proportion of zirconium nitrate and yttrium oxide so as to prepare the YSZ powder. The main purpose of adding zirconium nitrate is to provide zirconium element, and zirconium nitrate can be decomposed into zirconium oxide in the subsequent step; the main purpose of adding yttria is to provide yttrium element to the reactants.
S206, mixing the powder reagent and the molten salt solvent through a mixer to obtain a mixed material. And fully mixing the powder reagent and the molten salt solvent through a mixer. In addition, by controlling the temperature, the rotating speed and the time during mixing, the powder reagent and the molten salt solvent can be ensured to be fully mixed under proper conditions. Optionally, the ambient temperature during compounding is from 90 ℃ to 120 ℃; the rotating speed of the mixer is 100r/min to 200r/min in the mixing process; the mixing time is 2 to 10 hours. Alternatively, zirconium nitrate can be decomposed into zirconium oxide under the action of mechanical and thermal energy at an ambient temperature of 120 ℃, and the physical size of the substance becomes smaller due to the existence of ball milling during the mixing process. In the mixing process, the components tend to be homogenized, and the refinement of particles and microcosmic can be realized; during the mixing process, chemical reactions, such as decomposition reactions (the decomposition of zirconium nitrate into zirconium oxide) also occur.
And S208, sintering the mixed material at a second temperature threshold, and preserving heat for a second time threshold to obtain the intermediate material. Sintering is a process of converting a powdery material into a compact. After the powder is formed, the compact obtained by sintering is a polycrystalline material. The sintering process directly affects the grain size, pore size, and grain boundary shape and distribution in the microstructure, thereby affecting the properties of the material. Optionally, the mixed material is filled into a ceramic pot for sealing, and the ceramic pot filled with the mixed material is placed into a muffle furnace for sintering. Muffle furnace is box furnace. Optionally, during sintering, the ambient temperature is 750 ℃ to 950 ℃ and the incubation time is 4 hours to 20 hours. By controlling the temperature and the holding time during sintering, it is ensured that intermediate materials are prepared for subsequent steps. The temperature and the heat preservation time during sintering can be accurately controlled, and the forming size of the electrolyte material can be optimized to a certain extent.
S210, pouring the intermediate material into water, and obtaining the electrolyte material after the treatment process. Optionally, pouring the intermediate material into clear water, and obtaining the micro-nano YSZ powder through a series of treatment processes such as centrifugation, filtration, drying and the like. The micro-nano YSZ powder is the electrolyte material. The purpose of pouring the intermediate material into the clear water in this step is to remove the molten salt solvent.
In another embodiment, the metal halide further comprises sodium halide. Sodium halide is used as a main molten salt solvent, zirconium nitrate and yttrium oxide react in a liquid phase environment and a required product (intermediate material) is formed. Sodium halide as one of the solvents may act as a dispersing compound. In the subsequent step, the intermediate material is poured into water to remove the redundant molten salt solvent, so as to obtain a pure reaction product. Alternatively, the sodium halide is sodium chloride.
Further, the metal halide also includes potassium halide. The potassium halide is used as a main molten salt solvent, zirconium nitrate and yttrium oxide react in a liquid phase environment and a required product (intermediate material) is formed. In the subsequent step, the intermediate material is poured into water to remove the redundant molten salt solvent, so as to obtain a pure reaction product. Alternatively, the potassium halide is potassium chloride.
Further, the proportional relationship between the amount of sodium halide substance, the amount of potassium halide substance and the amount of lithium halide substance is (1 to 3): (1-4): (1-5).
Further, the amount of the substance of lithium halide is one eighth to five seventh of the amount of the substance of the molten salt solvent. By controlling the ratio of the amount of lithium halide in the molten salt solvent, on the one hand, it can be ensured that the molten salt solvent contains a sufficient amount of lithium halide (a sufficient amount of lithium element); on the other hand, excessive amounts of lithium halide species can be avoided, which is advantageous in cost control. Alternatively, the lithium halide is lithium chloride. The molten salt solvent comprises lithium chloride, and lithium chloride is taken as a nucleation point in the process of synthesizing the electrolyte material, so that the overall morphology is bowl-shaped, and nucleation in the sintering process is facilitated. In addition, as the molten salt solvent contains lithium element, the melting point can be lower when sintering is carried out, which is beneficial to realizing energy saving in the preparation process.
Further, the amount of sodium halide substance is one tenth to three fifths of the amount of molten salt solvent substance. By controlling the ratio of the amount of sodium halide in the molten salt solvent, on the one hand, it can be ensured that the molten salt solvent contains enough sodium halide; on the other hand, excessive amounts of sodium halide substances can be avoided, which is beneficial to cost control.
Further, the amount of the substance of potassium halide is one-ninth to two-thirds of the amount of the substance of the molten salt solvent. By controlling the ratio of the amount of potassium halide in the molten salt solvent, on the one hand, it can be ensured that the molten salt solvent contains enough potassium halide; on the other hand, excessive amounts of potassium halide substances can be avoided, which is beneficial to cost control.
In another embodiment, the lithium halide is lithium chloride. The molten salt solvent comprises lithium chloride, and lithium chloride is taken as a nucleation point in the process of synthesizing the electrolyte material, so that the overall morphology is bowl-shaped, and nucleation in the sintering process is facilitated.
In another embodiment, the sodium halide is sodium chloride. Sodium chloride is used as a main molten salt solvent and can play a role of dispersing a compound, so that zirconium nitrate and yttrium oxide react in a liquid phase environment to generate a required product (intermediate material).
In another embodiment, the potassium halide is potassium chloride. Potassium chloride is used as a main molten salt solvent, zirconium nitrate and yttrium oxide react in a liquid phase environment and a required product (intermediate material) is generated. In the subsequent step, the intermediate material is poured into water to remove the redundant molten salt solvent, so as to obtain a pure reaction product.
In another embodiment, the treatment process comprises centrifugation.
In another embodiment, the treatment process includes filtration. Pouring the intermediate material into water, and obtaining the electrolyte material after a series of treatment processes such as filtration and the like. The purpose of the filtration is, on the one hand, to remove impurities, ensuring the purity of the electrolyte material prepared; on the other hand, the particle size is screened, so that the micro-nano YSZ powder is ensured to be obtained, the forming size of the electrolyte material is optimized, and the requirements of micro-nano size and uniformity are met.
In another embodiment, the treatment process includes baking. Pouring the intermediate material into water, and obtaining the electrolyte material after a series of treatment processes such as drying and the like. The purpose of the drying is to remove water molecules to exclude extraneous factors.
In another embodiment, the second temperature threshold is 750 ℃ to 950 ℃. By controlling the temperature during sintering to 750-950 ℃, on one hand, the overhigh temperature can be avoided, which is beneficial to controlling the energy consumption; on the other hand, too low a temperature can be avoided, thereby ensuring that intermediate materials are prepared after sintering for use in subsequent steps. Since the molten salt solvent contains lithium element, the melting point can be lower (at least 750 ℃) when sintering is performed in the subsequent step, which contributes to energy saving in the manufacturing process.
In another embodiment, the second time threshold is 4h to 20h. The heat preservation time in the sintering process is controlled to be 4-20 hours, so that on one hand, the heat preservation time can be prevented from being too short, and the intermediate material is prepared after full sintering; on the other hand, the overlong heat preservation time of sintering can be avoided, so that the overall preparation efficiency is improved.
In a third embodiment according to the present invention, as shown in fig. 3, the steps of the method for preparing an electrolyte material of a solid oxide fuel cell include:
s302, preparing a molten salt solvent composed of metal halides, wherein the metal halides comprise lithium halides. The lava solvent is composed of a metal halide, and the metal halide includes lithium halide, so that the lava solvent has a lithium element. Among the binary compounds containing halogen, compounds in which halogen (halogen element including fluorine element, chlorine element, bromine element and iodine element) is negatively charged are called halides. The metallic halides and the nonmetallic halides are classified according to the properties of the constituent halide elements. Most of the alkali metal halides and alkaline earth metal halides are ionic, and are characterized by high melting point and boiling point, and are easily dissolved in water. Alternatively, the metal halide in this step is an ionic alkali metal halide and the intermediate material is poured into water in a subsequent step to remove the molten salt solvent. Optionally, lithium halide is combined with halides of other metals in a ratio of the amounts of the substances in the molten salt solvent. In the technical scheme defined by the invention, the electrolyte material is synthesized by adopting a molten salt method. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material in the subsequent step, the halide of lithium element is taken as a nucleation point, and the overall morphology is bowl-shaped, so that nucleation in the sintering process is facilitated. In addition, since the molten salt solvent contains lithium element, the melting point can be lower (may be 750 ℃ at the minimum) when sintering is performed in the subsequent step, contributing to energy saving in the manufacturing process.
S304, zirconium nitrate and yttrium oxide are mixed according to an atomic ratio of 100:4, mixing the components in proportion to obtain the powder reagent. And determining the atomic ratio of molecular formula after the pre-powder is formed by controlling the mixing proportion of zirconium nitrate and yttrium oxide so as to prepare the YSZ powder. The main purpose of adding zirconium nitrate is to provide zirconium element, and zirconium nitrate can be decomposed into zirconium oxide in the subsequent step; the main purpose of adding yttria is to provide yttrium element to the reactants.
S306, mixing the powder reagent and the molten salt solvent through a mixer at a first temperature threshold and a first rotation speed threshold for a first time threshold, and obtaining a mixed material. And fully mixing the powder reagent and the molten salt solvent through a mixer. In addition, by controlling the temperature, the rotating speed and the time during mixing, the powder reagent and the molten salt solvent can be ensured to be fully mixed under proper conditions. Optionally, the ambient temperature during compounding is from 90 ℃ to 120 ℃; the rotating speed of the mixer is 100r/min to 200r/min in the mixing process; the mixing time is 2 to 10 hours. Alternatively, zirconium nitrate can be decomposed into zirconium oxide under the action of mechanical and thermal energy at an ambient temperature of 120 ℃, and the physical size of the substance becomes smaller due to the existence of ball milling during the mixing process. In the mixing process, the components tend to be homogenized, and the refinement of particles and microcosmic can be realized; during the mixing process, chemical reactions, such as decomposition reactions (the decomposition of zirconium nitrate into zirconium oxide) also occur.
And S308, filling the mixed material into a ceramic pot for sealing, putting the ceramic pot filled with the mixed material into a muffle furnace for sintering at a second temperature threshold, and preserving heat for a second time threshold to obtain the intermediate material. Sintering is a process of converting a powdery material into a compact. After the powder is formed, the compact obtained by sintering is a polycrystalline material. The sintering process directly affects the grain size, pore size, and grain boundary shape and distribution in the microstructure, thereby affecting the properties of the material. Optionally, during sintering, the ambient temperature is 750 ℃ to 950 ℃ and the incubation time is 4 hours to 20 hours. By controlling the temperature and the holding time during sintering, it is ensured that intermediate materials are prepared for subsequent steps. The temperature and the heat preservation time during sintering can be accurately controlled, and the forming size of the electrolyte material can be optimized to a certain extent. The mixed material is filled into the ceramic pot for sealing, so that the mixed material is ensured not to react with the outside air in the sintering process, and irrelevant factors are eliminated. In addition, the ceramic pot filled with the mixed materials is placed into a muffle furnace for sintering, so that the sufficiency of the sintering process is ensured, and the intermediate materials are prepared for subsequent steps.
And S310, pouring the intermediate material into water, centrifuging, filtering and drying to obtain the electrolyte material. Optionally, pouring the intermediate material into clear water, and obtaining the micro-nano YSZ powder through a series of treatment processes such as centrifugation, filtration, drying and the like. The micro-nano YSZ powder is the electrolyte material. The purpose of pouring the intermediate material into the clear water in this step is to remove the molten salt solvent. The purpose of centrifugation is to effectively separate the different suspended particles. Further, the purpose of the filtration is, on the one hand, to remove impurities, ensuring the purity of the electrolyte material prepared; on the other hand, the particle size is screened, so that the micro-nano YSZ powder is ensured to be obtained, the forming size of the electrolyte material is optimized, and the requirements of micro-nano size and uniformity are met. Further, the purpose of the drying is to remove water molecules to exclude extraneous factors.
In another embodiment, the first temperature threshold is 90 ℃ to 120 ℃. The environment temperature during mixing is controlled to be 90-120 ℃, so that on one hand, the environment temperature is not too low, and the powder reagent and the molten salt solvent can be fully mixed under proper conditions; on the other hand, the environment temperature is not too high, which is beneficial to controlling the energy consumption.
In another embodiment, the first rotational speed threshold is 100r/min to 200r/min. The rotating speed of the mixer is controlled to be 100r/min to 200r/min, so that on one hand, the excessive high rotating speed of the mixer can be avoided, and the energy consumption can be controlled; on the other hand, the over-slow rotation speed of the mixer can be avoided, so that the powder reagent and the molten salt solvent can be fully mixed under the assistance of the mixer.
In another embodiment, the first time threshold is 2h to 10h. By controlling the mixing time to be 2-10 hours, on one hand, the too short mixing time can be avoided, so that the powder reagent and the molten salt solvent can be fully mixed under the assistance of a mixer; on the other hand, the overlong mixing time can be avoided, so that the overall preparation efficiency is improved.
In another embodiment, the ceramic tank is made of alumina. The ceramic tank is made of aluminum oxide, so that the mixed material which can be filled into the ceramic tank is sealed, and the mixed material is ensured not to react with the outside air in the sintering process, so that irrelevant factors are eliminated.
In another embodiment, the ceramic tank is made of zirconia. The ceramic tank is made of zirconia, so that the mixed materials which can be filled into the ceramic tank are sealed, and the mixed materials are prevented from reacting with outside air in the sintering process, so that irrelevant factors are eliminated.
In one embodiment according to the present invention, the electrolyte material of the solid oxide fuel cell is fabricated by the method of preparing the electrolyte material of the solid oxide fuel cell in any one of the embodiments described above. The electrolyte material prepared by the preparation method provided by the invention has uniform molding size and meets the requirements of micro-nano size and uniformity.
According to embodiments of the electrolyte material of the solid oxide fuel cell and the preparation method thereof, the electrolyte material is synthesized by adopting a molten salt method, and the preparation method is simple; in the second aspect, the forming size of the electrolyte material is optimized, and the requirements of micro-nano size and uniformity can be met. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material, the halide of lithium element is taken as a nucleation point, and the overall morphology is bowl-shaped, so that nucleation in the sintering process is facilitated. In addition, as the molten salt solvent contains lithium element, the melting point can be lower when sintering is carried out, which is beneficial to realizing energy saving in the preparation process.
Example 1
The method for preparing the electrolyte material of the solid oxide fuel cell comprises the following steps:
s402, preparing a molten salt solvent with lithium element. The molten salt solvent includes 1mol of sodium halide, 1mol of potassium halide, and 1mol of lithium halide. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material in the subsequent step, the halide of lithium element is taken as a nucleation point, and the overall morphology is bowl-shaped, so that nucleation in the sintering process is facilitated. In addition, since the molten salt solvent contains lithium element, the melting point can be lower (may be 750 ℃ at the minimum) when sintering is performed in the subsequent step, contributing to energy saving in the manufacturing process. In addition, the control of the ratio of the amounts of sodium halide, potassium halide and lithium halide is beneficial to the regulation of the melting temperature of the molten salt solvent and the promotion of the dispersion of the electrolyte material.
S404, preparation of zirconium nitrate Zr (NO) 3 ) 4 Yttria Y 2 O 3 Powder reagent is formed. The ratio of the amounts of zirconium nitrate to yttrium oxide material was 100:8. the main purpose of adding zirconium nitrate is to provide zirconium element, and zirconium nitrateCan be decomposed into zirconia in a subsequent step; the main purpose of adding yttria is to provide yttrium element to the reactants. The control of the crystal grain size of the yttria-stabilized zirconia electrolyte is facilitated by controlling the ratio of the amounts of the substances of zirconium nitrate and yttria.
S406, mixing the powder reagent with the molten salt solvent to obtain a mixed material. Optionally, mixing the powder reagent and the molten salt solvent through a mixer to obtain a mixed material. Optionally, the ambient temperature during compounding is 120 ℃; the rotating speed of the mixer is 105r/min in the mixing process; the mixing time is 3h. Alternatively, zirconium nitrate can be decomposed into zirconium oxide under the action of mechanical and thermal energy at an ambient temperature of 120 ℃, and the physical size of the substance becomes smaller due to the existence of ball milling during the mixing process. In the mixing process, the components tend to be homogenized, and the refinement of particles and microcosmic can be realized; during the mixing process, chemical reactions, such as decomposition reactions (the decomposition of zirconium nitrate into zirconium oxide) also occur.
And S408, sintering the mixed material to obtain an intermediate material. Sintering is a process of converting a powdery material into a compact. After the powder is formed, the compact obtained by sintering is a polycrystalline material. The sintering process directly affects the grain size, pore size, and grain boundary shape and distribution in the microstructure, thereby affecting the properties of the material. Optionally, the mixed material is filled into a ceramic pot for sealing, and the ceramic pot filled with the mixed material is placed into a muffle furnace for sintering. Muffle furnace is box furnace. Optionally, during sintering, the ambient temperature is 870 ℃, and the holding time is 5h.
S410, pouring the intermediate material into water, and obtaining the electrolyte material after the treatment process. Optionally, pouring the intermediate material into clear water, and obtaining the micro-nano YSZ powder through a series of treatment processes such as centrifugation, filtration, drying and the like. The micro-nano YSZ powder is the electrolyte material. YSZ represents a class of rare earth yttrium doped zirconia, also known as yttrium stabilized zirconia. The purpose of pouring the intermediate material into the clear water in this step is to remove the molten salt solvent.
Example 2
The method for preparing the electrolyte material of the solid oxide fuel cell comprises the following steps:
S502, preparing a molten salt solvent with lithium element. The molten salt solvent includes 2mol of sodium halide, 2mol of potassium halide, and 3mol of lithium halide. The molten salt solvent comprises lithium halide, and in the process of synthesizing the electrolyte material in the subsequent step, the halide of lithium element is taken as a nucleation point, and the overall morphology is bowl-shaped, so that nucleation in the sintering process is facilitated. In addition, since the molten salt solvent contains lithium element, the melting point can be lower (may be 750 ℃ at the minimum) when sintering is performed in the subsequent step, contributing to energy saving in the manufacturing process. In addition, the control of the ratio of the amounts of sodium halide, potassium halide and lithium halide is beneficial to the regulation of the melting temperature of the molten salt solvent and the promotion of the dispersion of the electrolyte material.
S504, preparation of zirconium nitrate Zr (NO) 3 ) 4 Yttria Y 2 O 3 Powder reagent is formed. The ratio of the amounts of zirconium nitrate to yttrium oxide material was 100:8.5. the main purpose of adding zirconium nitrate is to provide zirconium element, and zirconium nitrate can be decomposed into zirconium oxide in the subsequent step; the main purpose of adding yttria is to provide yttrium element to the reactants. The control of the crystal grain size of the yttria-stabilized zirconia electrolyte is facilitated by controlling the ratio of the amounts of the substances of zirconium nitrate and yttria.
S506, mixing the powder reagent with the molten salt solvent to obtain a mixed material. Optionally, mixing the powder reagent and the molten salt solvent through a mixer to obtain a mixed material. Optionally, the ambient temperature during compounding is 105 ℃; the rotating speed of the mixer is 150r/min in the mixing process; the mixing time is 8h. Alternatively, zirconium nitrate can be decomposed into zirconium oxide under the action of mechanical and thermal energy at an ambient temperature of 105 ℃, and a reduction in physical size of the substance can be generated due to the presence of ball milling during mixing. In the mixing process, the components tend to be homogenized, and the refinement of particles and microcosmic can be realized; during the mixing process, chemical reactions, such as decomposition reactions (the decomposition of zirconium nitrate into zirconium oxide) also occur.
And S508, sintering the mixed material to obtain an intermediate material. Sintering is a process of converting a powdery material into a compact. After the powder is formed, the compact obtained by sintering is a polycrystalline material. The sintering process directly affects the grain size, pore size, and grain boundary shape and distribution in the microstructure, thereby affecting the properties of the material. Optionally, the mixed material is filled into a ceramic pot for sealing, and the ceramic pot filled with the mixed material is placed into a muffle furnace for sintering. Muffle furnace is box furnace. Alternatively, during sintering, the ambient temperature is 800 ℃ and the incubation time is 8 hours.
S510, pouring the intermediate material into water, and obtaining the electrolyte material after the treatment process. Optionally, pouring the intermediate material into clear water, and obtaining the micro-nano YSZ powder through a series of treatment processes such as centrifugation, filtration, drying and the like. The micro-nano YSZ powder is the electrolyte material. YSZ represents a class of rare earth yttrium doped zirconia, also known as yttrium stabilized zirconia. The purpose of pouring the intermediate material into the clear water in this step is to remove the molten salt solvent.
In the present invention, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; the term "plurality" means two or more, unless expressly defined otherwise. The terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; "coupled" may be directly coupled or indirectly coupled through intermediaries. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the description of the present invention, it should be understood that the directions or positional relationships indicated by the terms "upper", "lower", "left", "right", "front", "rear", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or units referred to must have a specific direction, be constructed and operated in a specific direction, and thus should not be construed as limiting the present invention.
In the description of the present specification, the terms "one embodiment," "some embodiments," "particular embodiments," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. A method for preparing an electrolyte material for a solid oxide fuel cell, comprising:
preparing a molten salt solvent with lithium element;
preparing a powder reagent consisting of zirconium nitrate and yttrium oxide;
mixing the powder reagent with the molten salt solvent to obtain a mixed material;
sintering the mixed material to obtain an intermediate material;
and pouring the intermediate material into water, and obtaining the electrolyte material after a treatment process.
2. The method for producing an electrolyte material for a solid oxide fuel cell according to claim 1, characterized in that the preparation of a molten salt solvent having a lithium element, specifically:
preparing the molten salt solvent consisting of metal halides including lithium halide, sodium halide and potassium halide.
3. The method for producing an electrolyte material for a solid oxide fuel cell according to claim 2, wherein a proportional relationship among the amount of the sodium halide substance, the amount of the potassium halide substance, and the amount of the lithium halide substance is (1 to 3): (1-4): (1-5).
4. The method for producing an electrolyte material for a solid oxide fuel cell according to claim 2, wherein the lithium halide is lithium chloride; or the sodium halide is sodium chloride; or the potassium halide is potassium chloride.
5. The method for producing the electrolyte material for a solid oxide fuel cell according to any one of claims 1 to 4, wherein the production of the powder reagent composed of zirconium nitrate and yttrium oxide, specifically, is:
mixing the zirconium nitrate and the yttrium oxide according to an atomic ratio of 100:4, mixing the components in proportion to obtain the powder reagent.
6. The method for preparing an electrolyte material of a solid oxide fuel cell according to any one of claims 1 to 4, wherein the powder reagent and the molten salt solvent are mixed to obtain a mixed material, specifically:
and mixing the powder reagent and the molten salt solvent through a mixer to obtain the mixed material.
7. The method for preparing an electrolyte material of a solid oxide fuel cell according to claim 6, wherein the powder reagent and the molten salt solvent are mixed by a mixer to obtain the mixed material, specifically:
and mixing the powder reagent and the molten salt solvent through the mixer at a first temperature threshold and a first rotation speed threshold, and obtaining the mixed material.
8. The method for producing an electrolyte material for a solid oxide fuel cell according to claim 7, wherein the first temperature threshold is 90 ℃ to 120 ℃.
9. The method for producing an electrolyte material for a solid oxide fuel cell according to claim 7, wherein the first rotation speed threshold value is 100r/min to 200r/min.
10. The method for producing an electrolyte material for a solid oxide fuel cell according to claim 7, wherein the first time threshold is 2h to 10h.
11. The method for preparing an electrolyte material for a solid oxide fuel cell according to any one of claims 1 to 4, wherein the step of sintering the mixture material provides an intermediate material, in particular:
sintering the mixed material at a second temperature threshold, and preserving heat for a second time threshold to obtain the intermediate material.
12. The method for producing an electrolyte material for a solid oxide fuel cell according to claim 11, wherein the second temperature threshold value is 750 ℃ to 950 ℃.
13. The method for producing an electrolyte material for a solid oxide fuel cell according to claim 11, wherein the second time threshold is 4h to 20h.
14. The method for preparing an electrolyte material for a solid oxide fuel cell according to claim 11, wherein the step of sintering the mixture at a second temperature threshold and maintaining the mixture for a second time threshold is performed to obtain the intermediate material, specifically:
and filling the mixed material into a ceramic pot for sealing, putting the ceramic pot filled with the mixed material into a muffle furnace for sintering at the second temperature threshold, and preserving heat for the second time threshold to obtain the intermediate material.
15. The method for producing an electrolyte material for a solid oxide fuel cell according to claim 14, wherein the material of the ceramic can is alumina.
16. The method for producing an electrolyte material for a solid oxide fuel cell according to claim 14, wherein the material of the ceramic can is zirconia.
17. The method for preparing an electrolyte material for a solid oxide fuel cell according to any one of claims 1 to 4, wherein the step of pouring the intermediate material into water and performing a treatment process to obtain the electrolyte material comprises the following steps:
pouring the intermediate material into water, centrifuging, filtering and drying to obtain the electrolyte material.
18. An electrolyte material for a solid oxide fuel cell, characterized by being produced by the method for producing an electrolyte material for a solid oxide fuel cell according to any one of claims 1 to 17.
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